•Supported Co catalysts for SBH and AB hydrolysis prepared by magnetron sputtering.•Deposition conditions were varied to improve catalytic activity.•Decrease in power and increase pressure produces more amorphous and disperse catalysts.•Durability upon cycling was studied for both hydrolysis reactions.•Acid reactivation was effective for sodium borohydride but not for ammonia borane.

Supported Co catalysts were prepared for sodium borohydride and ammonia borane hydrolysis by magnetron sputtering for the first time under different conditions. Ni foam was selected as support. Deposition conditions (time, pressure, and power) were varied to improve catalytic activity. A decrease in deposition power from 200 to 50 W, leads to a decrease in crystallite and column size and a higher activity of catalysts. The increase in deposition pressure from 1.5 × 10−2 to 4.5 × 10−2 mbar produces same effect but in this case the enhancement in activity is higher because amorphous materials were obtained. The highest activity for SB hydrolysis was 2650 ml min−1 gcat−1 for the 50 W Co 4.5 (4 h) sample (Ea = 60 ± 2 kJ mol−1). For AB hydrolysis activity for the 50 W Co 3.2 (4 h) sample was similar. Durability of the thin films was tested for both reactions upon cycling (14 cycles). Diluted acid washing was effective to recover the activity for sodium borohydride reaction but not for ammonia borane hydrolysis. The strong Co–NH3 interactions explain the non-efficiency of the acid washing.